Shifting away from fossil- to biobased feedstocks is an important step towards a more sustainable materials sector. Isosorbide is a rigid, glucose-derived secondary diol, which has been shown to impart favourable material properties, but its low reactivity has hampered its use in polyester synthesis. Here we report a simple, yet innovative, synthesis strategy to overcome the inherently low reactivity of secondary diols in polyester synthesis. It enables the synthesis of fully biobased polyesters from secondary diols, such as poly(isosorbide succinate), with very high molecular weights (M_n up to 42.8 kg/mol). The addition of an aryl alcohol to diol and diacid monomers was found to lead to the in-situ formation of reactive aryl esters during esterification, which facilitated chain growth during polycondensation to obtain high molecular weight polyesters. This synthesis method is broadly applicable for aliphatic polyesters based on isosorbide and isomannide and could be an important step towards the more general commercial adaption of fully biobased, rigid polyesters.

从化石原料转向生物基原料是迈向更可持续的材料行业的重要一步。异山梨醇是一种刚性的、葡萄糖衍生的仲二醇，已被证明具有良好的材料性能，但其低反应性阻碍了其在聚酯合成中的应用。在这里，我们报告了一种简单但创新的合成策略，以克服聚酯合成中仲二醇固有的低反应性。它能够从仲二醇合成完全生物基聚酯，例如聚（异山梨醇琥珀酸酯），具有非常高的分子量（M _n高达 42.8 千克/摩尔）。发现将芳基醇添加到二醇和二酸单体中会导致在酯化过程中原位形成反应性芳基酯，从而促进缩聚过程中的链增长以获得高分子量聚酯。这种合成方法广泛适用于基于异山梨醇和异甘露醇的脂肪族聚酯，可能是朝着全生物基刚性聚酯更普遍的商业化应用迈出的重要一步。